Detection of Low-Concentration Biological Samples Based on a QBIC Terahertz Metamaterial Sensor.

Quasi-bound state in the continuum (QBIC) can effectively enhance the interaction of terahertz (THz) wave with matter due to the tunable high-Q property, which has a strong potential application in the detection of low-concentration biological samples in the THz band. In this paper, a novel THz metamaterial sensor with a double-chain-separated resonant cavity structure based on QBIC is designed and fabricated. The process of excitation of the QBIC mode is verified and the structural parameters are optimized after considering the ohmic loss by simulations. The simulated refractive index sensitivity of the sensor is up to 544 GHz/RIU, much higher than those of recently reported THz metamaterial sensors. The sensitivity of the proposed metamaterial sensor is confirmed in an experiment by detecting low-concentration lithium citrate (LC) and bovine serum albumin (BSA) solutions. The limits of detection (LoDs) are obtained to be 0.0025 mg/mL (12 µM) for LC and 0.03125 mg/mL (0.47 µM) for BSA, respectively, both of which excel over most of the reported results in previous studies. These results indicate that the proposed THz metamaterial sensor has excellent sensing performances and can well be applied to the detection of low-concentration biological samples.

Synthesis and catalytic performance of wood cellulose nanofibers grafted with polylactic acid in rare-earth complexes based on tetrazole carboxylic acids.

Stannous octanoate [Sn(Oct)2] and 4-dimethylamino pyridine (DMAP) were used to catalyze the synthesis of amphiphilic cellulose-based graft copolymers, but the acute toxicity of tin ions and DMAP prompts the need for the application of less harmful catalysts. Herein, green catalyst complexes 1-3 [M(H0.5L)2(H2O)5]·2(H2O) (M = Sm, 1; M = Nd, 2; M = Eu, 3; H2L = 4-(3-(tetrazol-5-yl)pyridin-5-yl)benzoic acid) were synthesized, and their properties were systematically investigated. Single-crystal X-ray diffraction showed that the complexes possessed a zero-dimensional structure, while the thermogravimetry and scanning electron microscopy results confirmed their stability after heating at 110 °C for 10 h. Using complexes 1-3 and DMAP as the catalysts, CNFs were grafted with l-lactide via homogeneous ring-opening polymerization to form wood cellulose nanofibers grafted with l-lactide (WGLAs), and the effects of the ratio of wood cellulose nanofibers (WCNFs) to l-lactide ([AGU]/[LA]) and catalyst dosage were studied. The polymerization followed the coordination-insertion mechanism. Under comparable reaction conditions, the grafting ratio of WGLA-1 reached 84.7 %, and the grafting ratio of complex 1 was found to be higher than those achieved using DMAP. WGLAs demonstrated good thermal stability without cytotoxicity, and the residual catalysts in the WGLAs exhibited fluorescence characteristics. Overall, amphiphilic cellulose-based materials with fluorescence emission offered a promising modification strategy to prepare high-performance polymer composites for agriculture and biomedical application.

Hydrazylpyridine salicylaldehyde-copper(II)-1,10-phenanthroline complexes as potential anticancer agents: synthesis, characterization and anticancer evaluation.

We synthesized and analyzed nine unique copper(II) hydrazylpyridine salicylaldehyde and 1,10-phenanthroline complexes, [Cu(L1a)(phen)] (Cugdupt1), [Cu(L2a)(phen)]·(CH3CN) (Cugdupt2), [Cu(L3a)(phen)] (Cugdupt3), [Cu(L4a)(phen)]·(CH3CN) (Cugdupt4), [Cu(L5a)(phen)] (Cugdupt5), [Cu(L6a)(phen)] (Cugdupt6), [Cu(L7a)(phen)] (Cugdupt7) [Cu(L8a)(phen)] (Cugdupt8) and [Cu(L9a)(phen)]·0.5(H2O) (Cugdupt9). We were motivated by the intriguing properties of the coupled ligands of hydrazylpyridine, salicylaldehyde, and 1,10-phenanthroline. The MTT assay demonstrated that Cugdupt1-Cugdupt9 have higher anticancer activity than L1H2-L9H2, phen and cisplatin on A549/DDP cancer cells (A549cis). Cugdupt1-Cugdupt9 were superior to cisplatin with IC50 values of 1.6-100.0 fold on A549cis cells (IC50(Cugdupt1-Cugdupt9) = 0.5-30.5 µM, IC50(cisplatin) = 61.5 ± 1.0 µM). However, Cugdupt1-Cugdupt9 had lower cytotoxicity toward the HL-7702 normal cells. Cugdupt1 and Cugdupt8 can induce reduction of mitochondrial respiratory chain complexes I/IV (MRCC-I/IV), mitophagy pathways, and eventually protein regulation and adenosine triphosphate (ATP) depletion in A549cis cells. The findings indicated that Cugdupt1 and Cugdupt8 caused cell death via both ATP diminution and mitophagy pathways. Finally, Cugdupt8 demonstrated high efficacy and no obvious cytotoxicity in A549 tumor-bearing mice. This study thus helps evaluate the potential of the hydrazylpyridine salicylaldehyde-copper(II)-1,10-phenanthroline compounds for cisplatin-resistant tumor therapy.

Wood Cellulose Nanofibers Grafted with Poly(ε-caprolactone) Catalyzed by ZnEu-MOF for Functionalization and Surface Modification of PCL Films.

Renewable cellulose nanofiber (CNF)-reinforced biodegradable polymers (such as polycaprolactone (PCL)) are used in agriculture, food packaging, and sustained drug release. However, the interfacial incompatibility between hydrophilic CNFs and hydrophobic PCL has limited further application as high-performance biomaterials. In this work, using a novel ZnEu-MOF as the catalyst, graft copolymers (GCL) with CNFs were grafted with poly(ε-caprolactone) (ε-CL) via homogeneous ring-opening polymerization (ROP), and used as strengthening/toughening nanofillers for PCL to fabricate light composite films (LCFs). The results showed that the ZnEu-MOF ([ZnEu(L)2(HL)(H2O)0.39(CH3OH)0.61]·H2O, H2L is 5-(1H-imidazol-1-yl)-1,3-benzenedicarboxylic acids) was an efficient catalyst, with low toxicity, good stability, and fluorescence emissions, and the GCL could efficiently promote the dispersion of CNFs and improve the compatibility of the CNFs and PCL. Due to the synergistic effect of the ZnEu-MOF and CNFs, considerable improvements in the mechanical properties and high-intensity fluorescence were obtained in the LCFs. The 4 wt% GCL provided the LCF with the highest strength and elastic modulus, which increased by 247.75% and 109.94% compared to CNF/PCL, respectively, showing the best elongation at break of 917%, which was 33-fold higher than CNF/PCL. Therefore, the ZnEu-MOF represented a novel bifunctional material for ROP reactions and offered a promising modification strategy for preparing high-performance polymer composites for agriculture and biomedical applications.